Dyeing process and dyes

ABSTRACT

PCT No. PCT/GB96/00867 Sec. 371 Date Jan. 30, 1998 Sec. 102(e) Date Jan. 30, 1998 PCT Filed Apr. 9, 1996 PCT Pub. No. WO96/35012 PCT Pub. Date Nov. 7, 1996A process for defining a substrate is provided. The process comprises applying to the substrate a water soluble dye having at least two electrophilic groups and a nucleophilic agent having a molecular weight below 600 and at least one group selected from aliphatic primary amino groups and secondary amino groups.

This invention relates to a process for dyeing substrates, to dyes andto compositions.

In conventional dyeing processes using water-soluble dyes, not all dyefixes to a substrate and, after dyeing, the dyehouse has the expensiveproblem of disposing of highly coloured solutions containing unfixeddye. For example, during normal exhaust dyeing some unfixed dye remainsin the dyebath, whilst some only loosely adheres to textiles and has tobe washed-off in the dyehouse to avoid later cross-staining of adjacentfibres during domestic washing. This can result in large volumes ofcoloured effluent which often contains considerable amounts of dissolveddye. There is a need for a dyeing process which results in colourless orweakly coloured effluent and, ideally, coloured textiles which requireless or no washing after dyeing is complete. Such a process would makedyehouses more environmentally friendly and reduce their effluentdisposal costs.

According to a first aspect of the present invention there is provided aprocess for the coloration of a substrate comprising applying thereto awater-soluble dye having at least two electrophilic groups and anucleophilic agent having a molecular weight below 600 and at least onegroup selected from aliphatic primary amino groups and aliphaticsecondary amino groups.

The dye and the nucleophilic agent may react together during the processto form a highly substantive species which has great affinity for thesubstrate. The precise mechanism is not fully understood, but thespecies might exist as some form of oligomer or polymer wherein theagent and dye are joined together by either covalent bonds formedbetween the electrophilic groups of the dye and aliphaticprimary/secondary group(s) in the nucleophilic agent, or by anion-cationattraction between anionic groups in the dye (when present) and cationicprotonated aliphatic primary and secondary amino groups. Possibly bothof these mechanisms play a part in formation of the highly substantivespecies.

It is possible to select appropriate combinations of dyes andnucleophilic agents for use in the process by measuring how much dye isimmobilised under exhaust dyeing conditions. Very high immobilisationunder these conditions indicates that the dye and nucleophilic agentform the highly substantive species and this behaviour is reflected inother dyeing processes, e.g. printing, continuous and semi-continuousdyeing.

Preferably the dye and the nucleophilic agent used in the process aresuch that if they are applied to cotton by exhaust dyeing at least 90%,more preferably at least 95%, especially at least 97%, more especiallyfrom 99% to 100% of the dye is immobilised. This definition is notintended to limit processes of the invention to exhaust dyeing, butserves as a useful test for identifying combinations of dyes andnucleophilic agents which can react together and form a highlysubstantive species under a whole variety of different dyeingconditions.

The extent of immobilisation of the dye may be determined by dissolving0.100 grammes ("W1") of dye in a dyebath containing 30 ml of waterbuffered at pH 7, adding 0.75 g of sodium sulphate and 5 g of cotton,heating to 95° C. over one hour, maintaining the temperature at 95° C.for one hour, then adding nucleophilic agent such that the ratio ofelectrophilic groups in the dye to the total amount of aliphatic primaryamino groups and aliphatic secondary amino groups in the nucleophilicagent is 2:3, heating for one further hour at 95° C., followed byremoving the dyed cotton from the dyebath and stirring the dyed cottonfor 15 minutes with each of (i) 50 ml of water containing 0.03 grammesof acetic acid, and (ii) three lots of 50 ml of boiling water, whereinthe total weight in grammes of dye dissolved in the dyebath and washesis determined using a spectrophotometer ("W2") and the % immobilisationis given by the calculation:

    [(W1-W2)÷W1]×100%

When some combinations of dye and agent are heated under exhaust dyeingconditions in the presence of a substrate they form not only a highlysubstantive species on the substrate but also a solid precipitate whichcan fall to the bottom of the dyebath. Under these circumstances the %immobilisation is still calculated as described above because theprecipitate is not actually dissolved in the dyebath. The presence of aprecipitate in the dyebath is usually acceptable because it can easilybe removed by filtration, thereby lowering the chemical content of dyeliquors which are disposed of after dyeing. However, to avoid wastingdye it is preferred that the amount of precipitate formed in the dyebathis less than 10%, more preferably less than 5%, especially less than 2%,more preferably 0% by weight relative to the weight of dye used.

A valuable feature of the present coloration process is that the dye andnucleophilic agent may be joined together without the need for freeradical initiators. The process can operate using aqueous solutions ofthe dye and nucleophilic agent at practical temperatures using normaldyeing equipment. In one embodiment the molecular weight of thenucleophilic agent is below 600 and at least 50 below that of the dye.

As will be understood, the electrophilic groups in the water-soluble dyeare required to react with aliphatic primary and/or secondary aminogroups in the nucleophilic agent (this allows formation of a highlysubstantive species). Thus where the water-soluble dye is a reactive dyethe process for coloration is performed under conditions such that thedye does not react to a significant extent with the substrate (e.g. <10%reacts, preferably <5%) before it reacts with the nucleophilic agent.Hence the present process is distinct from a simple post-dyeing aftertreatment involving contacting a substrate dyed with a reactive dye(wherein dye has lost its reactive groups) with a nucleophilic agent.Conditions where the dye does not react to a significant extent with thesubstrate before it can react with the nucleophilic agent can beselected by dyers without difficulty, for example high pH and hightemperatures tend to encourage covalent bond formation between reactivedyes and cellulosic substrates and would therefore be avoided.

The Dye

Preferably the dye has from 2, 3, 4, 5, or 6 electrophilic groups. Theelectrophilic groups may be any group capable of forming a covalent bondwith the nucleophilic agent during the coloration process. Preferablysaid electrophilic group is a group capable of undergoing 1) asubstitution reaction, 2) an addition reaction or 3) an elimination andaddition reaction with the aforementioned nucleophilic agent.

Preferred groups capable of undergoing a substitution reaction are ofthe formula --COCH₂ --X¹, --COCHR¹ CH₂ --X¹, --COCHX¹ CHX¹ CO₂ R²,--COCHX¹ CHX¹ COR¹, --CH₂ --X¹ and --NHCOCH₂ --X¹

wherein:

X¹ is a labile group;

R¹ is H or a labile group;

R² is H or optionally substituted alkyl, aryl or heteroaryl; and

X¹ is preferably halo, especially chloro, bromo or iodo.

A labile group is a group displaceable by the aliphatic primary orsecondary amino group in the aforementioned nucleophilic agent when thedye is heated or basified.

When R¹ is a labile group it is preferably halo, especially chloro.

The optional substituents which may be present on R² are preferably asmentioned hereinafter for L². R² is preferably H, phenyl or C₁₋₄ -alkyl,especially methyl or ethyl.

A further group capable of undergoing a substitution reaction is alabile group attached to a heterocycle, for example a triazine ring. Thelabile group is preferably chloro or fluoro, or a quaternary ammoniumgroup such as optionally substituted pyridinium.

Groups which are capable of undergoing an addition reaction preferablycomprise an epoxide group, an aziridine, aziridinium, azetidine orcyclopropane group or, more preferably, an activated alkene (e.g.alkenyl sulphone) or alkyne capable of undergoing a Michael-typeaddition with the aforementioned nucleophilic group.

A preferred activated alkene is or comprises a group of formula --Z¹--CR³ ═CR⁴ R⁵, --CR³ ═CR⁵ --Z² or --CZ² ═CR³ R⁵ wherein Z¹ and Z² areelectron withdrawing groups and R³, R⁴ and R⁵ are each independently H,C₁₋₄ -alkyl or halo. Z¹ is preferably --SO--, --SO₂ --, --CO--,especially --SO₂ --, and Z² is preferably --CN, --NO₂ or an alkyl- orarylsulphonyl group or an acyl group. The activated alkene of formula--Z¹ --CR³ ═CR⁴ R⁵ may be attached to a group of formula --NR² --(wherein R² is as hereinbefore defined) to give a group of formula --NR²--SO--CR³ ═CR⁴ R⁵, --NR² --SO₂ --CR³ ═CR⁴ R⁵ or --NR² --CO--CR³ ═CR⁴ R⁵.Preferred alkylsulphonyl groups are --SO₂ --(C₁₋₄ -alkyl) and preferredarylsulphonyl groups are phenylsulphonyl and tosyl. Preferred acylgroups are of the formula --CO--R² wherein R² is as hereinbeforedefined, especially C₁₋₄ -alkyl or phenyl. It is preferred that R³ andR⁴ are both H.

Examples of activated alkenes include the following: ##STR1##--NHCOCBr═CH₂, --CO--CBr═CHBr, ##STR2## --SO₂ --CH═CH₂, --SO--CH═CH₂,--COCCl═CCl₂, --SO₂ CH═CHCl, --CH═CH--CN, --CH═CH--NO₂, --C(CN)═CH₂,--NHSO₂ --CH═CH₂, --N(CH₃)SO₂ CH═CH₂, --C(NO₂)═CH₂ and ##STR3##

A preferred group capable of undergoing an elimination and additionreaction is or comprises a group of the formula --Z¹ --NR² --(CR⁶R⁶)_(m) --X² or --Z¹ (CR⁶ R⁶)_(m) --X², especially --Z¹ --NH--CH₂ --CH₂--X² and --Z¹ --CH₂ --CH₂ --X² wherein X² is a labile group; Z¹ and R²are as hereinbefore defined; each R⁶ independently is halo, --NH₂,carboxy or a group described above for R² ; and m is 2, 3 or 4.Preferably the labile group represented by X² is --OSO₃ H, --SSO₃ H,--OPO₃ H₂, or a salt thereof, halo (especially chloro) or acetoxy. Thegroups of formula --Z¹ (CR⁶ R⁶)_(m) --X² may be attached to a group offormula --NR² -- as defined above, in which case the CR⁶ R⁶ groups maybe replaced by CHR⁶ groups.

Examples of groups capable of undergoing an elimination and additionreaction include the following:

--SO₂ CH₂ CH₂ OSO₃ H, --SO₂ (CH₂)₃ OSO₃ H, --SO₂ CH₂ CH₂ Cl, --SO₂ CH₂CH₂ OPO₃ H₂, --NHCOCH₂ CH₂ OSO₃ H, --SO₂ CH₂ CH₂ OCOCH₃, --SOCH₂ CH₂OSO₃ H, --SO₂ CH₂ CH₂ SSO₃ H, --NHSO₂ CH₂ CH₂ OSO₃ H, --NHSO₂ (CH₂)₃SSO₃ H, --NHSO₂ (CH₂)₄ OSO₃ H, --N(CH₃)SO₂ CH₂ CH₂ OSO₃ H, --SO₂NH--CH(CH₃)CH₂ --OSO₃ H, --SO₂ NH--CH(CH₂ CH₃)CH₂ --OSO₃ H, --SO₂NH--C(OH)(CH₃)CH₂ --OSO₃ H, --SO₂ NH--CH(CH₃)CH(Ph)--OSO₃ H, --SO₂NHCH(OSO₃ H)CH₂ --OSO₃ H, --SO₂ NHCH(COOH)CH₂ OSO₃ H, --SO₂ NHCH(Ph)CH₂OSO₃ H, --SO₂ NHCH₂ CH₂ Cl, --SO₂ NHC(CH₃)₂ CH₂ OSO₃ H, --SO₂ NHC(CH₂OSO₃ H)₃, --SO₂ NHCH₂ CH₂ Br, --SO₂ NHCH₂ CH₂ OSO₃ H, --SO₂NHC(CH₃)(OH)CH₂ OSO₃ H and --SO₂ NH(CH₂)₃ --OSO₃ H.

In one embodiment the aforementioned groups of formula --Z¹ --NR² --(CR⁶R⁶)_(m--X) ², --NR² --Z¹ (CR⁶ R⁶)_(m) --X², --Z¹ --CR³ ═CR⁴ R⁵, --CR³═CR⁵ --Z² and --CZ² ═CR³ R⁵ are attached directly to an aromatic carbonatom, for example the carbon atom of an aromatic ring such as a benzenering, in molecules of the dye.

Particularly good results are found where the electrophilic group is anactivated alkene or a group capable of undergoing an elimination andaddition reaction, especially vinyl sulphones and groups which areconvertible to vinyl sulphones on treatment with aqueous alkali.

Preferably the dye is capable of absorbing radiation at a wavelength inthe region from the ultraviolet to the infra-red, preferably in thevisible region of the spectrum, especially light of a wavelength from400 to 700 nm. Preferably the dye has an extinction coefficient of atleast 5,000, more preferably at least 10,000, especially from 10,000 to300,000, more especially from 10,000 to 150,000.

The dye can contain any chromophore. The dye is preferably an azo,anthraquinone, phthalocyanine, triphenodioxazine, triphenylmethane,formazan, xanthene or benzdifuranone dye or a dye which contains acombination of these chromophores, especially an azo dye.

Preferred azo dyes contain 1,2,3 or 4 azo (--N═N--) groups. Preferablythe dye has high substantivity as this greatly enhances immobilisationof the dye when it reacts with the nucleophilic agent.

According to a preferred embodiment of the present invention the dye hasthe Formula (1) or is a salt thereof: ##STR4## wherein: each Q¹independently is a labile or non-labile substituent;

each T independently is --O--, --S-- or --NR^(a) --;

each L¹ independently is a divalent organic linker group;

each V¹ independently is a group which is capable of undergoing anaddition reaction or an elimination and addition reaction;

each R^(a) independently is H or optionally substituted alkyl;

Z is the residue of a coupling component; and

m and n are each independently 0 or 1.

By "labile substituent" it is meant an atom or group attached directlyto the triazine ring which is displaceable by the hydroxy group of acellulosic material under alkaline conditions. The preferred labile atomis a halogen, especially Cl or F. The preferred labile group is sulpho,more preferably a quaternary ammonium group. As examples of quaternaryammonium groups there may be mentioned trialkyl ammonium groups andoptionally substituted pyridinium groups, especially 3-carboxypyridiniumand 4-carboxypyridinium.

Non-labile substituents represented by each Q¹ include groups of formula--NR⁷ R⁸ and --OR⁷ wherein R⁸ is H or alkyl and R⁷ is H, optionallysubstituted alkyl or optionally substituted aryl. Preferably R⁸ is H oroptionally substituted C₁₋₄ -alkyl and R⁷ is H, optionally substitutedC₁₋₄ alkyl or optionally substituted phenyl.

Preferably each T independently is --NR^(a) -- wherein R^(a) is ashereinbefore defined.

The divalent organic linker group represented by each L¹ is preferablyan optionally substituted or interrupted alkylene group containing from2 to 10 carbon atoms, especially C₂₋₄ -alkylene, or more preferably anoptionally substituted C₆₋₁₁ arylene group, more preferably optionallysubstituted phenylene or naphthylene.

Preferred groups represented by V¹ which are capable of undergoing anaddition reaction or an elimination and addition reaction are asdescribed in International Patent Application No. PCT/GB93/02344, page6, line 13 to page 8, line 18, which is included herein by referencethereto. Preferably each V¹ independently is a vinyl sulphone group or agroup which is convertible to a vinyl sulphone group on treatment withan aqueous alkali, or a group of formula

--SO₂ NHCH₂ CH₂ --Y wherein Y is --OSO₃ H, --SSO₃ H, --Cl or --OCOCH₃.

Each R^(a) is preferably H or C₁₋₄ -alkyl, especially H, methyl orethyl.

The residue of a coupling component represented by Z is preferably anoptionally substituted buta-1,3-dione, phenylene, naphthylene orheterocyclic group (e.g. a pyrazolone), more preferably Z is optionallysubstituted 1,3- or 1,4-phenylene.

When L¹, Z, R^(a), R⁷ or R⁸ is substituted it is preferred that eachsubstituent is selected from amino, alkyl (preferably C₁₋₄ -alkyl)alkoxy (preferably C₁₋₄ -alkoxy), amido (preferably --NHCOC₁₋₄ -alkyl),cyano, ureido, sulpho, carboxy, hydroxy, nitro and halo.

Preferably m and n have a value of 1. When m and n are 1 it is preferredthat the sulpho groups shown in formula (1) (and for that matter inFormula (2) below) are both ortho with respect to the --CH═CH-- group.

A preferred dye of Formula (1) is of Formula (2) and salts thereof:##STR5## wherein: each R^(b) independently is H or C₁₋₄ -alkyl;

G is H, alkyl, alkoxy, amido, ureido, halo, nitro, carboxy, amino orsulpho;

each Q² independently is F, Cl or a quaternary ammonium group; and

each V² independently is a vinyl sulphone group or a group which isconvertible to a vinyl sulphone group on treatment with aqueous alkali,or a group of formula --O₂ NHCH₂ CH₂ -- wherein Y is --OSO₃ H, --SSO₃ H,--Cl or --OCOCH₃, or a group of formula:

    --NHCOCR.sup.b ═CH.sub.2 or --NHCOCBr═CH.sub.2.

G is preferably H, C₁₋₄ -alkyl, C₁₋₄ -alkoxy, --NHCOC₁₋₄ -alkyl orureido, more preferably H, methyl, methoxy, ureido or --NHCOCH₃.

The V² groups shown in Formula (2) are preferably at the 3- or4-position relative to the --NR^(b) -- group.

Groups which are convertible to a vinyl sulphone group (i.e. --SO₂CH═CH₂) on treatment with aqueous alkali include --SO₂ CH₂ CH₂ OSO₃ H,--SO₂ CH₂ CH₂ SSO₃ H, --SO₂ CH₂ CH₂ OCOCH₃ and --SO₂ CH₂ CH₂ Cl.

The dyes of Formula (1) can be applied to substrates in conjunction witha nucleophilic agent to give high levels of colour and good fastness towater.

The dyes of Formula (1) may be prepared by condensing a compound ofFormula (7) with about two molar equivalents of a compound: ##STR6## ofFormula (8) wherein Z, R^(a), T, V¹, L¹, X^(a), Q¹, m and n are ashereinbefore defined and Y' is a labile group (preferably Cl or F).

In the above process it is preferred to use about two molar equivalentsof the compound of Formula (8) relative to the compound of Formula (7)because using more or less is wasteful of whichever compound is inexcess. Normally, therefore, one will use from 1.5 to 2.5, preferablyfrom 1.8, particularly from 2.0, to 2.2, molar equivalents of thecompound of Formula (8). The condensation is preferably performed in anaqueous solvent, especially water. A temperature of 20 to 40° C. ispreferred, and a reaction time of 2 to 48 hours is convenient.

The compound of Formula (7) may be prepared by diazotising a suitable4amino-4'-nitro-stilbene derivative, coupling onto a coupling component(e.g. an aniline compound) and reducing the nitro group. The compound ofFormula (8) can be prepared by condensing an appropriate triazinecompound with a compound of Formula H--T--L¹ --V wherein T,L¹ and V areas hereinbefore defined.

The Nucleophilic Agent

In the first aspect of the invention, the nucleophilic agent has amolecular weight below 600 and at least one group selected fromaliphatic primary amino groups and aliphatic secondary amino groups. Inone embodiment of the first aspect, the nucleophilic agent has amolecular weight in the range 60 to 599, more preferably 100 to 550.

Preferably the nucleophilic agent of the first aspect has at least twoaliphatic primary or secondary amino groups because this is believed togive a highly substantive polymer in which the dye and agent constitutealternative units. However in some cases, depending on the dye andagent, reaction of the two or more electrophilic groups in the dye withnucleophilic agents having only one aliphatic primary or secondary aminogroup can produce a highly substantive species.

The aliphatic primary amino group is an amino of group formula --NH₂attached to a nitrogen atom or an aliphatic carbon atom and an aliphaticsecondary amino group is a group of formula --NH-- attached to twoaliphatic carbon atoms or to one aliphatic carbon atom and one nitrogenatom.

It is believed important that the --NH₂ and --NH-- groups in aliphaticprimary and secondary amino groups are attached to aliphatic carbonatoms because attachment to aromatic species (e.g. phenyl or naphthyl)or to a carbonyl group (--CO--) lowers the nucleophilicity of the --NH₂or --NH-- group thereby rendering them less reactive towardselectrophilic groups in the dye under practical conditions. There may ofcourse be amine groups in the nucleophilic agent which are not aliphaticprimary or secondary amino groups provided the nucleophilic agent has atleast one group, preferably at least two groups, selected from aliphaticprimary amino and aliphatic secondary amino groups.

The aliphatic primary amino groups and secondary amino groups may beattached to the same carbon atom, for example as found in guanidinegroups such as --NH-- C(═NH)--NH₂ and --NH--C(═NH)--NH--. In hydrazinesthere can be one aliphatic primary amino group and one aliphaticsecondary amino group, for example as in CH₃ NH--NH₂, two aliphaticsecondary amino groups, for example as in CH₃ NH--NHCH₃, or twoaliphatic primary amino groups, for example as in H₂ NN(CH₂ CH₂)₂ NNH₂.

Preferred aliphatic primary amino groups are of the formula --CH₂ --NH₂,--CH(R⁹)--NH₂ and --C(R⁹)₂ --NH₂ and preferred aliphatic secondary aminogroups are of the formula --CH₂ --NH--CH₂ --, --CH(R⁹)--NH--CH₂ -- and--CH(R⁹)--NH--CH(R⁹)-- wherein each R⁹ independently is H or optionallysubstituted alkyl, aryl or aralkyl, more preferably H or C₁₋₄ -alkyl,especially H or methyl.

Examples of the nucleophilic agents of the first aspect includecompounds having 1 aliphatic primary amino group and no aliphaticsecondary amino groups, e.g. methylamine, ethylamine, propylamine, H₂NCH₂ CH₂ SH; Compounds having 2 aliphatic primary amino groups and noaliphatic secondary amino groups, e.g. H₂ NCH₂ CH₂ NH₂, H₂ N(CH₂)₃ NH₂,H₂ N(CH₂)₄ NH₂, H₂ N(CH₂)₆ NH₂, H₂ N(CH₂)₈ NH₂, 1,2- and1,3-diaminocyclohexane, H₂ NCH(CH₃)CH₂ NH₂, H₂ NCH₂ CH(NH₂)CO₂ H, H₂NCH₂ CH(CH₂ CH₃)NH₂, Ph--CH(NH₂)--CH(NH₂)--Ph, H₂ NCH₂ C(CH₂ CH₃)₂ CH₂NH₂, H₂ NCH₂ CHOHCH₂ NH₂, H₂ NCH₂ COCH₂ NH₂, H₂ NCH₂ C(CH₃)₂ CH₂ NH₂, H₂NCH₂ CH₂ N(CH₂ CH₂)₂ NCH₂ CH₂ NH₂, H₂ N(CH₂)₃ N(CH₂ CH₂)₂ N(CH₂)₃ NH₂,H₂ N(CH₂)₄ N(CH₂ CH₂)₂ N(CH₂)₄ NH₂ and compounds of formula H₂ NCH₂ CH₂(OCH₂ CH₂)_(n) NH₂ wherein n is from 1 to 9; Compounds having threealiphatic primary amino groups and no aliphatic secondary amino groups,for example 1,2,3-triaminopropane and (H₂ NCH₂ CH₂)₃ N; Compounds havingone aliphatic primary amino group and one aliphatic secondary aminogroup, for example (CH₃)₂ CH--NHCH₂ CH₂ NH₂, CH₃ NHCH₂ CH₂ NH₂, CH₃ CH₂NHCH₂ CH₂ NH₂, HOCH₂ CH₂ NHCH₂ CH₂ NH₂, (CH₃ O)₃ Si(CH₂)₃ NHCH₂ CH₂ NH₂,(CH₃)₂ NCH₂ CH₂ NHCH₂ CH₂ NH₂, (CH₃ CH₂)₂ NCH₂ CH₂ NHCH₂ CH₂ NH₂, PhCH₂NHCH₂ CH₂ NH₂, (CH₃)₂ CHNHCH(CH₃)CH₂ NH₂, 3-aminopyrrolidine,3-aminopiperidine, 2-aminomethylpiperidine, O₂ CCH₂ NHCH₂ CH₂ NH₂,cyclohexanyl--NH--CH₂ CH₂ NH₂ and H₂ N(CH₂)₃ NH(CH₂)₃ NHCOCH₃ ;Compounds having two aliphatic primary amino groups and one aliphaticsecondary amino group, for example H₂ N(CH₂ CH₂ NH)₂ H, H₂ NCH₂ CH₂NH(CH₂)₂ NH₂, H₂ NCH₂ CH₂ NH(CH₂)₄ NH₂ and NH(CH₂ CH(CH₃)--NH₂)₂ ;Compounds having a least two aliphatic secondary amino groups,especially from 2 to 8 secondary amino groups, for example HO(CH₂ CH₂NH)₂ CH₂ CH₂ OH, HO₂ CCH₂ NHCH₂ CH₂ NHCH₂ CO₂ H, PhCH₂ NHCH₂ CH₂ NHCH₂Ph, (--NHCH₂ CH₂ --)₃,4 or 5, piperazine, 2-methylpiperazine, 2,5- and2,6-dimethylpiperazine, H₂ N(CH₂ CH₂ NH)_(n) H wherein n is 3,4 or 5,CH₃ NHCH₂ CH₂ NHCH₃, (--NHCH₂ CH₂ CH₂ --)₄,1,4,7,10,13-(6-hexaazacyclooctadecane), (CH₃ O)₃ Si(CH₂ CH₂ NH)₂ CH₂ CH₂CO₂ CH₃ and (CH₃ O)₃ Si(CH₂ CH₂ NH)₂ CH₂ CH₂ NH₂.

In a further aspect of the invention, when a dye of Formula (1) above,or a salt thereof is employed, it has advantageously been found that thenucleophilic agent is not restricted to the nucleophilic agents of thefirst aspect, although such agents can be employed in certain beneficialembodiments. Accordingly, a further aspect of the present inventionprovides a process for the coloration of a substrate comprising applyingthereto a dye of Formula (1) and a nucleophilic agent having at leastone, more preferably at least two, groups selected from thiols, thiones,aliphatic primary amino groups and aliphatic secondary amino groups.

In one embodiment of this further aspect, the nucleophilic agent has amolecular weight below 600 and in another the molecular weight is atleast 600. The thiols, thiones, aliphatic primary amino groups andaliphatic secondary amino groups in the nucelophilic agent used in thefurther aspect are believed to react with the groups represented by V¹or V² in dyes of Formula (1) to give a highly substantive species whichhas a strong affinity for substrates and low solubility in water.

The thiol (i.e. --SH) group which may be present in the nucleophilicagent used in the further aspect may, for example, be present in asubstituent of formula --CO--SH or --NH--CO--SH used.

The thione group which may be present in the nucleophilic agent used inthe further aspect is of the formula ═S, for example as found in--PS(--OH)₂ and --O--PS(--OH)₂ and --O--PS(--OH)₂. A preferred thionegroup is of the formula >C═S, for example the agent may have a --CS--OH,--CS--NH₂, --NH--CS--OH or thiourea substituent. Preferred thione groupsare of the formula --NR^(b) --CS--NR^(b) R^(b) or --NR^(b) --CS--NR^(b)-- wherein each R^(b) independently is as hereinbefore defined, providedat least one R^(b) is H.

In one embodiment, the nucleophilic agent used in the further aspect hasa quaternary amine group, in addition to the one or more groups selectedfrom thiols, thiones, aliphatic primary amino groups and aliphaticsecondary amino groups. The quaternary amine group can in many casesincrease affinity of the nucleophilic agent for substrates such ascotton leading to stronger dyeings and higher wash fastness. Examples ofquaternary amine groups include dialkyl phenyl ammonium, e.g. Ph(CH₃)₂N⁺ --, Ph(CH₃ CH₂)₂ N⁺ --; optionally substituted pyridinium, e.g. 2-,3- and 4-methyl pyridinium, 2-, 3-, 4-carboxy pyridinium;N-alkyl-pyridinyloxy, e.g. N-methyl-4-pyridinyloxy,N-methyl-2-pyridinyloxy and N-ethyl-4-pyridinyloxy; tri(alkyl)ammonium,e.g. (CH₃)₃ N⁺ --, (CH₃ CH₂)₃ N⁺ --, CH₃ (CH₃ CH₂)₂ N⁺ --; (CH₂)₅ N⁺ --;(CH₂ CH₂ OCH₂ CH₂)N⁺ --; and those derived from quinuclidine anddiazobicyclo octane.

The thiol or thione group which may be present in the nucleophilic agentused in the further aspect can be attached to a heterocyclic ring,preferably a 5 or 6 membered ring containing 1, 2 or 3 atoms selectedfrom nitrogen, oxygen and sulphur, to give what are hereinafter referredto as heterocyclic thiol or thione groups respectively. The preferredheterocyclic thiol or thione group contains 1, 2 or more preferably 3nitrogen atoms. Preferred heterocyclic thiol or thione groups carry 1 or2 groups selected from --SH and ═S. Examples of heterocyclic thiols andthiones include groups for Formula (3) and (4): ##STR7##

The groups of Formula (3), Formula (4) and the thioureas may exist intautomeric forms other than those illustrated and these are included inthe present invention. By way of illustration tautomers of groups ofFormula (3) include those illustrated below by Formulae (3a) and (3b)and tautomers of groups of Formula (4) include those illustrated by(4a), (4b), (4c) and (4d): ##STR8##

The nucleophilic agent used in the further aspect is preferably atriazine compound having 1, 2 or 3 groups selected from thiols andthiones, especially trithiotriazine (i.e. s-triazine having three --SHgroups) or a group of the formula:

    A--X.sup.a --W--X.sup.a --A

wherein:

each A is a group of Formula (4) as hereinbefore defined;

each X^(a) independently is oxygen, sulphur or --NR^(c) --;

each R^(c) independently is H or alkyl; and

W is a divalent organic linker group.

R^(c) is preferably H or C₁₋₄ -alkyl.

W is preferably an alkylene, arylene or aralkylene group. The preferredalkylene group is optionally substituted C₂₋₄ -alkylene. The preferredarylene group is optionally substituted phenylene or naphthylene. Thepreferred aralkylene group is optionally substituted benzylene orxylylene. When W is substituted the substituent(s) are preferablyselected from halo, especially chloro; nitro; alkoxy, especially C₁₋₄-alkoxy; alkyl, especially C₁₋₄ -alkyl; cyano; hydroxy; --SH; amino; Wmay contain or be free from chromophores.

Another preferred nucleophilic agent in the further aspect is of Formula(5) or (6): ##STR9## wherein each R¹⁰ independently is H or optionallysubstituted alkyl, preferably H or C₁₋₄ -alkyl; each W independently isas hereinbefore defined; and each Q³ is a quaternary amine group.Preferred quaternary amine groups are as hereinbefore described. Anotherpreferred nucleophilic agent is of formula Q³ --W--CH₂ SH wherein Q³ andW are as hereinbefore defined.

Imine nucleophilic agents having a molecular weight of at least 600which can be employed in the further aspect include polyethylene imine("PEI") 600, PEI 1000, PEI 1800, PEI 60,000 and PEI 100,000.

In both the first aspect and the further aspect of the presentinvention, the nucleophilic agent is preferably water soluble.

It is possible to select particularly valuable combinations of dyes ofFormula (1) and nucleophilic agents for use in the process by measuringhow much dye is immobilised under exhaust dyeing conditions. Very highimmobilisation under these conditions indicates that the dye andnucleophilic agent form a highly substantive species and this behaviouris reflected in other dyeing processes, e.g. printing, continuous andsemi-continuous dyeing.

The dye having at least two electrophilic groups and the nucleophilicagent may be applied to the substrate in either order or simultaneously.Preferably said dye is applied to the substrate before the nucleophilicagent as this allows the dye to colour the substrate evenly before beingfixed by the nucleophilic agent.

A preferred process according to the invention for coloration of asubstrate comprises the steps:

(a) applying an aqueous solution of a dye having at least twoelectrophilic groups to the substrate;

(b) bringing a nucleophilic agent having a molecular weight below 600and at least one group selected from aliphatic primary amino groups andaliphatic secondary amino groups into contact with the substrate.

A process according to the further aspect invention for the colorationof a substrate comprises the steps:

(a) applying a dye of Formula (1) above to the substrate.

(b) bringing a nucleophilic agent into contact with the substrate.

A convenient way of performing step (a) is to immerse the substrate inan aqueous solution of said dye. Step (b) may be achieved by adding thenucleophilic agent to the aqueous solution.

In another process, steps (a) and (b) are employed as described aboveexcept that said dye is used in step (b) in place of the nucleophilicagent, and said nucleophilic agent is used in step (a) in place of thedye.

The simultaneous application of the dye having at least twoelectrophilic groups and the nucleophilic agent is particularly usefulwhere said dye and the nucleophilic agent do not react together veryquickly at ambient temperature or neutral pH and an elevated temperatureand/or pH is required to make the two species react. In this case saiddye has the opportunity to colour the substrate evenly before fixing byraising the temperature and/or pH.

The nucleophilic moieties in the nucleophilic agent, particularly whenthe nucleophilic moieties are amine groups, can be masked using aprotecting group if so desired. In this way, particularly storage stablecompositions comprising the dye having at least two electrophilic groupsand a masked nucleophilic agent can be provided. The protecting groupcan be removed from the nucleophilic agent before, during or after ithas been applied to a substrate, for example by treating the agent withacid, base or by heating it. Examples of protecting groups which can beused to mask the nucleophilic agent include CF₃ CO, CH₃ CO and all otherknown protecting groups for nucleophilic moieties, particularly fornitrogen and sulphur nucleophiles.

The amount of said dye in the aqueous solution will depend upon thedepth of shade required and solubility of the dye. Typically the aqueoussolution contains 0.001% to 40% by weight of the dye relative to theweight of water, preferably 0.01% to 30% more preferably 0.01% to 5%.

The ratio of dye to the nucleophilic agent or masked nucleophilic agent(by weight) applied to the substrate is preferably in the range 100:1 to1:100, more preferably 20:1 to 1:20, particularly 19:1 to 1:19,especially 9:1 to 1:9, more especially 3:1 to 1:3. Factors influencingthe preferred ratio include the relative molecular weights of the dyeand nucleophilic agent, the number of electrophilic groups in the dyeand the number of nucleophilic moieties, for example, thiol, thione,aliphatic primary and secondary amino groups in the nucleophilic agent.Because the dye and nucleophilic agent are believed to join together byreaction of the electrophilic groups in the dye (V groups in a dye ofFormula (1)) and the nucleophilic moieties for example thiol, thioneand/or amino groups in the nucleophilic agent, it is preferred that therelative amounts (in moles) of dye and nucleophilic agent is chosen suchthat the total number of nucleophilic moieties, including thiol, thione,aliphatic primary and secondary amino groups, is about equal to orexceeds the number of electrophilic groups, and when dyes of Formula (1)are employed, is preferably about equal, e.g. in the range 5:4 to 4:5.However, if one wishes the dye may be used in excess such thatfibre-reactive electrophilic groups remain present which can formcovalent bonds with cellulosic substrates in a conventional manner.

The dye and the nucleophilic agent are preferably applied to thesubstrate as an aqueous solution, more preferably as a solution inwater. In the process for the coloration of a substrate according to thefirst or second aspects of the invention, comprising applying thereto adye and a nucleophilic agent as hereinbefore decribed, the dye andnucleophilic agent are preferably heated and/or basified thereby causingthe dye and nucleophilic agent to react together.

During the process for coloration of a substrate it is preferred to heatand/or basify the substrate either before step (a), during step (a),between step (a) and step (b), during step (b), after step (b), or anycombination thereof. Heating and/or basifying during step (a) can beuseful to exhaust dye onto the substrate before bringing thenucleophilic agent into contact with the product of step (a), forexample at the same temperature or, for economy, at a lower temperature.Preferably the aqueous solution of dye containing at least twoelectrophilic groups is applied to the substrate at an elevatedtemperature, (e.g. at a temperature between 40° C. and 300° C.,preferably 45° C. and 200° C., especially 45° C. and 140° C.) and thenucleophilic agent is applied to the substrate at a lower temperature(e.g. at a temperature between 0° C. and 110° C., preferably 10° C. and85° C.).

The heating may be achieved by any means, for example by an electricalmeans such as a heating mantle, infra-red, microwave or ultrasound or byusing steam.

When the present process is performed by basifying a mixture of said dyeand nucleophilic agent it is preferred that the basifying is from afirst pH to a second pH at least 0.5 pH units higher than the first pH,more preferably at least 1 pH unit higher, especially at least 2 pHunits higher, more especially at least 3 pH units higher and optionallyup to 7 pH units higher than the first pH. The first pH is preferablybetween pH 0 and pH 8.5, more preferably between pH 2 and pH 8,especially between pH 4 and pH 8, more especially between pH 6 and pH 8and especially preferably approximately pH 7.

Preferably basification is achieved using an alkaline earth or alkalimetal, base or salt, more preferably an alkali metal hydroxide,carbonate or bicarbonate, especially a sodium or potassium hydroxide,carbonate, bicarbonate or composition thereof. In some cases thenucleophilic agent is sufficiently basic to avoid the need for any otherbase being added.

Although formulae have been shown in their unionised or free acid formin this specification, for example --SO₃ H, these formulae include theionised and salt forms, particularly salts with alkali metals such assodium, potassium or lithium or mixed sodium/lithium salts, ammoniumsalts and salts where the nucleophilic agent acts as a cation.

A further feature of the present invention provides a compositioncomprising:

(i) a dye having at least two electrophilic groups; and

(ii) a nucleophilic agent or masked nucleophilic agent, the nucelophilicagent having, in unmasked form, a molecular weight below 600 and atleast one group selected from aliphatic primary amino groups andaliphatic secondary amino groups.

A particularly preferred composition comprises:

(i) a dye of Formula (1); and

(ii) a nucleophilic agent having at least one group selected fromthiols, thiones, aliphatic primary amino groups and aliphatic secondaryamino groups.

The preferred dye and nucleophilic agents contained in the compositionsare as hereinbefore described in relation to the present process. Thepreferred ratio of dye to nucleophilic agent is as hereinbeforedescribed. The composition may contain one or more of the dyes and oneor more of the nucleophilic agents.

In the present process it is preferred that the composition is heatedfrom a first temperature to a second temperature at least 20° C. higherthan the first temperature, more preferably at least 30° C. higher,especially at least 40° C. higher and optionally up to 200° C. or 300°C. higher than the first temperature. The first temperature ispreferably between 0° C. and 40° C., more preferably between 5° C. and40° C., especially between 10° C. and 40° C. The composition may beheated by any means, for example by an electrical means such as aheating mantle, infra-red, microwave or ultrasound or by using steam.The heating may be done at neutral, acid or alkali pH, preferably at apH above 7. The composition may be basified by adding an alkalinesolution of the dye to nucleophilic agent, by adding an alkalinesolution nucleophilic agent to the dye, or by adding alkaline earth oralkali metal, base or salt to a solution of the composition.

In one embodiment of the present process, the composition contains abuffer which maintains the pH in the range 5 to 8.5, more preferably 6to 8. The use of a buffer can lead to dyeings which are more level. Asexamples of suitable buffers there may be mentioned phosphate, borateand citrate buffers, especially Na₂ HPO₄, K₂ HPO₄ and sodiumtripolyphosphate.

As there is no need to use a free-radical initiator in the presentprocess it is preferred that the process is performed in the absence ofsuch an initiator.

The dyes of Formula (1) may also be applied to substrates byconventional methods used for reactive dyes, for example exhaust,continuous, semi-continuous and pad-batch dyeing and printing. Thus thedye of Formula (1) can be applied to a substrate, preferably inconjunction with an acid-binding agent, especially an alkali metalhydroxide, carbonate or bicarbonate. In one process an aqueous solutionof the dye of Formula (1) or salt thereof is applied to a substrate at atemperature between 70° C. and 140° C. (preferably between 90° C. and131° C.), the temperature is lowered to a temperature between 50° C. and70° C. (preferably between 55° C. and 65° C.) and an acid-binding agentis added to the aqueous solution.

Dyes used in the process may be prepared by analogous methods to thosedescribed in the dyestuff art except that intermediates are selectedwhich will result in the dye having the aforementioned electrophilicgroups.

Alternatively, dyes according to the invention containing an azochromophore may be prepared by coupling two suitable precursors.

The substrate used in the process is preferably leather or a textilematerial, especially a natural, semi-synthetic or synthetic material.

Examples of natural textile materials include wool, silk, hair andcellulosic materials, particularly cotton, jute, hemp, flax and linen.Preferred cotton materials are Sea Island, Egyptian, American, Peruvian,Asiatic and Indian cottons, for example cottons having a staple lengthof 2.5 to 5 cm, a denier of 1 to 2 and a moisture content of at least8%.

Examples of synthetic and semi-synthetic materials include polyamides,polyesters, polyacrylonitriles and polyurethanes.

A further feature of this invention comprises a polymer or oligomerobtained or obtainable by heating or basifying or heating and basifyinga composition according to the present invention. Preferably the heatingand/or basifying is from first to second temperatures and pHs asdescribed hereabove.

The invention is further illustrated by the following examples in whichall parts and percentages are by weight unless otherwise stated.

In the following Examples the extent of immobilisation (%) wasdetermined by the method described earlier in the specification. Allλmax were recorded in water.

EXAMPLE 1 Stage (a)--Dye Preparation Preparation of ##STR10##

A solution of 4(β-sulphatoethylsulphonyl) aniline (6.2 g) in water (50ml) was adjusted to pH 6 using 2N sodium carbonate. 2N sodium nitrite(12 ml) was added and the solution was cooled in ice, then added to amixture of ice and concentrated hydrochloric acid (6 ml). After stirringat 0-5° C. for 2 hours excess nitrous acid was destroyed by the additionof sulphamic acid to give a diazo component.

The suspension of diazo component was added to a solution of5,5'-dihydroxydinaphth-2,2'-yl-urea-7,7'-disulphonic acid (5.5 g) inwater (150 ml) at pH 3 and 0-5° C. After stirring for 30 minutes, thesolution was allowed to warm to room temperature. An approximately equalvolume of iso-propanol was added to the mixture and the resultant orangeprecipitate was filtered off to give the title product (6.7 g) havingtwo electrophilic groups and a λmax at 482 nm.

Stage (b)--Dyeing Process

The title product (0.10 g) was dissolved in water (30 ml) containing pH7 buffer and sodium sulphate (0.75 g). A piece of cotton (5 g) was addedand the solution was heated from 30° C. to 90° C. at the rate of 1degC.min⁻¹. After 30 minutes at 90° C. tris(2-aminoethyl)amine (0.05Msolution, 1.2 ml, a nucleophilic agent having three aliphatic primaryamino groups and no aliphatic secondary amino groups) was added andheating was continued at 90° C. for a further hour. The resultantdyebath was colourless and the cotton was dyed bright orange withexcellent wash-fastness.

Stage (c)--Further Dyeing Processes

The method stage (b) was varied as indicated below to give high fastnessdyeings:

as stage (b) but using piperazine in place of tris(2-aminoethyl)amine,

as stage (b) but using 1,4-diaminobutane in place oftris(2-aminoethyl)amine,

as stage (b) but using NaCl in place of sodium sulphate,

as stage (b) but heating to 60° C. instead of 90° C.,

as stage (b) but heating to 120° C. instead of 90° C.

EXAMPLE 2 Stage (a)--Dye Preparation ##STR11##

Cyanuric chloride (3.53 g) was dissolved in acetone (30 ml) and added toice water (50 ml). 1-hydroxy-6-aminonaphthalene-3-sulphonic acid("J-acid", 5 g) was dissolved in water (50 ml) at pH 6.5 and addeddropwise to the cyanuric chloride suspension, maintaining the mixture atpH 2 and a temperature of 0-5° C. After stirring for 3 hours, a further5 g of J-acid in water (50 ml) at pH 6.5 was added and the resultantmixture was stirred at room temperature and pH 6 overnight, and finallyat 40° C. for 2 hours. The mixture was cooled and the product salted outto give 18.5 g of a coupling component.

4-(β-sulphatoethylsulphonyl)aniline (3.55 g) was dissolved in water (50ml) at pH 7, and 7 ml of a 2M solution of sodium nitrite was added. Thissolution was added to ice water (50 ml) and concentrated HCl (4 ml) anddiazotised at 0-5° C. for 2 hours. Excess nitrous acid was destroyedusing sulphamic acid and the suspension was adjusted to pH 3. The abovecoupling component (4.0 g) was dissolved in water (100 ml) and addeddropwise at pH 3. After stirring at 0-5° C. for 2 hours, the solutionwas allowed to warm to room temperature overnight. Propan-2-ol was addedand the precipitate filtered off and dried to give the title dye havingtwo electrophilic groups (4.9 g) and λmax at 481 nm.

Stage (b)--Dyeing Process

The title product was applied to cotton using the method described inExample 1, stage (b). The resultant dyebath was colourless and thecotton was dyed a bright orange with excellent wash-fastness.

EXAMPLE 3

The method of Example 2 was followed except that in place of4-(β-sulphatoethylsulphonyl)aniline there was used2-methoxy-5-(β-sulphatoethylsulphonyl)aniline. The resultant dye wasapplied to cotton using the method of Example 1, stage (b), to give abrilliant yellowish-red dyeing with excellent wash-fastness.Furthermore, the dyebath was colourless at the end of dyeing.

EXAMPLE 4 Stage (a)--Dye Preparation ##STR12##

4-Nitroaniline (2.76 g) was stirred in ice water (100 ml) containingconcentrated HCl (6 ml) and 2M NaNO₂ solution (11 ml) was slowly added.The solution was stirred at 0-5° C. for 1.5 hours and excess nitrousacid was destroyed by the addition of sulphamic acid. Carbonyl J-acid(5.48 g) was dissolved in water (200 ml) and added dropwise to the diazosolution at pH 3-4. The reaction was then stirred at pH 3-4 and 0-5° C.for 3 hours before allowing to warm to room temperature overnight. Theresultant precipitate was filtered off, washed with a small amount ofwater and dried to give 10 g of a diazo dinitro compound.

The diazodinitro compound (5 g) was stirred in water (100 ml) at pH 8and room temperature. Sodium sulphide nonahydrate (7.09 g) and sodiumbicarbonate (2.5 g) were mixed in water and added to the solution. Afterstirring for 2 hours, the solution was carefully acidified to pH 2 withconcentrated HCl and the precipitate filtered off and dried to give 5.0g of a diamino diazo compound.

Cyanuric chloride (1.72 g) was dissolved in acetone (30 ml) and added toice water (50 ml). 3-(β-sulphatoethylsulphonyl)aniline (2.5 g) wasdissolved in water (50 ml) at pH 7 and added dropwise to the cyanuricchloride dispersion at pH 2-3 and 0-5° C. The reaction was stirred at0-5° C. and pH 2 for 2 hours. The above diamino diazo compound (3.5 g)was dissolved in water (100 ml) at pH 7 and was added at pH 7 and roomtemperature. The reaction was stirred at pH 7 overnight, then 10% w/vNaCl was added. The precipitate was filtered off and dried to give thetitle product (4 g) as a bluish-red dye having a λmax at 509 nm.

Stage (b)--Dyeing Process

The title dye (0.10 g) was dissolved in water (30 ml), and cotton (5 g)was added. The bath was heated from 30° C.-90° C. over 1 hour and sodiumsulphate (0.75 g) was added. After a further 30 minutes,tris(2-aminoethyl)amine(0.0024 g) was added and the dyebath heated at90° C. for 1 hour. The exhausted dyebath was completely colourless andthe cloth was dyed in a dull purple shade with excellent wash-fastness.

EXAMPLE 5 Preparation of ##STR13## Stage (a)

4-Amino-4'-nitro-2,2'-stilbene-disulphonic acid (69% strength, 28 g) wasdissolved in ice/water (200 g) and conc. HCl (12 ml), and then NaNO₂solution (2M, 24 ml) was added dropwise whilst maintaining thetemperature below 5° C. After stirring for 1/2 hour, excess nitrous acidwas destroyed using sulphamic acid and 3-methyl aniline (5 g) in acetone(50 ml) was added. The pH was raised to 5-6 using 2M NaOH and theproduct was filtered off and dried to give a monoazo solid (29 g).

The monoazo solid (7.0 g) was dissolved in water at pH 8 and a solutionof sodium sulphide hydrate (8.7 g) in water (50 ml) was added. Themixture was stirred for 3 hours, the pH was adjusted to 5 and a 10% w/vsalt solution was added. The resultant precipitate was filtered off anddried to give 6.3 g of solid.

Stage (b)

A solution of cyanuric chloride (2.28 g) in acetone (100 ml) was addedover 10 minutes to a solution of 4-(β-sulphatoethyl sulphonyl)aniline(3.45 g) in water (100 ml) at 0-5° C. After 1 hour the product of stage(a) (3.0 g) in water (100 ml) was added and the mixture was stirred atambient temperature for 14 hours. A 10% w/v salt solution was added andthe resultant precipitate was filtered off, washed with isopropanol anddried to give the title product (5.1 g) having a λmax at 407 nm.

Stage (c)--Dyeing

The title dye (0.1 g) was stirred in an aqueous pH 7 buffer solution (30ml) and the mixture was heated to 50° C. at a rate of 1° C. per minute.A piece of cotton (5 g) was added and the temperature was raised to 90°C. at a rate of 1° C. per minute. Sodium sulphate (0.75 g) was addedand, after 30 minutes, tris(2-aminoethyl) amine (1.05 ml, 0.05Msolution) was added and the temperature was maintained at 90° C. for 1hour. The cotton was dyed an attractive reddish yellow shade, leavingthe liquors essentially colourless.

The extent of immobilisation (measured using the test described earlierin the specification) was found to be 99.5%.

EXAMPLE 6

The method of Example 5 was repeated except that in place of3-methylaniline there was used 3-methyl-6-methoxy aniline. The resultantproduct had a λmax at 446 nm.

EXAMPLE 7

The method of Example 5 was repeated except that in place of3-methylaniline there was used 3-ureido aniline. The resultant producthad a λmax at 423 nm.

EXAMPLE 8

The method of Example 4 was repeated except that in place of3-(β-sulphatoethylsulphonyl)aniline there was used4-(β-sulphatoethylsulphonyl) aniline. The resultant dye had a λmax at517 nm.

EXAMPLE 9 Stage (a)--Dye Preparation ##STR14##

The title dye was prepared by the general method of Example 1 exceptthat in place of 4-(β-sulphatoethylsulphonyl)aniline there was used6-(β-sulphatoethylsulphonyl)-2-naphthylamine. The title dye had a λmaxat 504 nm.

Stage (b)--Dyeing Procedure

The product from stage (a) (0.20 g) was dissolved in pH 7 buffer (50 ml)and cotton (5 g) was added. The mixture was heated to 95° C. over 1hour, left for 15 minutes, Na₂ SO₄ (1.25 g) was added and the mixturewas then kept at 95° C. for a further hour. The cotton was removed fromthe essentially colourless dye liquor and cut into two.

One half of the cotton was stirred for 1 hour at 90° C. in a mixture ofwater (25 ml) and 1,4-diaminopiperazine solution (0.05M, 1.5 ml). Theother half was stirred in a mixture of water (25 ml) and (H₂ NCH₂ CH₂)₃N solution (0.05M, 2 ml). In both cases the amine solutions were onlyweakly coloured.

When the immobilisation test described earlier was performed using thetitle dye (0.100 g) and tris(2-aminoethyl)amine (0.013 g) animmobilisation of 97% was observed.

EXAMPLE 10 ##STR15## Stage (a)

Cyanuric chloride (4.06 g) was dissolved in acetone (30 ml) and added toice/water (50 ml). To this was added a solution of J-acid (4.78 g) inwater (100 ml), maintaining the mixture at pH 2-3 and 0-5° C. Themixture was stirred for a further 3 hours at 0-5° C. to give asuspension of J-acid dichlorotriazine.

2-methoxy-5-(β-sulphatoethylsulphonyl)aniline (6.22 g) was dissolved inwater (50 ml) at pH 7 with 2N sodium nitrite (11 ml). This was added toice and conc. hydrochloric acid (6 ml) and diazotised at 0-5° C. for 2hours. Excess nitrous acid was destroyed by the addition of sulphamicacid. The resultant diazo mixture was added dropwise to the suspensionof J-acid dichlorotriazine at pH 3-4 and stirred at room temperature for40 hours. The product was filtered off and dried to give a reddishpowder (14.7 g).

Stage (b)

4.8 g of the product from stage (a) was stirred in water (150 ml) at pH6.5 and room temperature. 4,4'-diaminostilbene-2,2'-disulphonic acid(0.99 g) in water (100 ml) was added and the solution was stirred at pH6-7 for 40 hours. The product was precipitated out by the addition ofpropan-2-ol, filtered off and dried to give 4.3 g of the title dye as areddish-orange powder with λmax at 489 nm.

Stage (c)--Dyeing

The title dye (0.10 g) was dissolved in pH 7 buffer solution (30 ml),cotton was added and the mixture was heated from 30° C. to 90° C. at 1degC.min⁻¹. Sodium sulphate (0.75 g) was added, and the bath was held at90° C. for a further 30 minutes. Tris(2-aminoethyl)amine (0.013 g) wasadded and the bath was heated at 90° C. for 1 hour. The exhausteddyebath was essentially colourless, and the cloth was dyed brightyellowish-red with excellent wash fastness.

EXAMPLE 11 ##STR16## Stage (a)

4-(β-Sulphatoethylsulphonyl)aniline (28.1 g) was dissolved in water (150ml), adjusted to pH 6 and 55 ml of 2N sodium nitrile was added. Thissolution was added to a mixture of ice and concentrated HCl (25 ml) anddiazotised at 0-5° C. for 2 hours. Excess nitrous acid was destroyed bythe addition of sulphamic acid. M-Toluidine (10.7 g) in ethanol (100 ml)was added to the diazo suspension and the mixture was stirred at 0-5°C., pH 3-4 for 2 hours before warming to room temperature. The productwas filtered-off and dried to give4-amino-2-methyl-4'-(β-sulphatoethylsulphonyl)azobenzene (31.9 g).

The above product (4.80 g) was dissolved in a mixture of water (75 ml)and tetrahydrofuran (50 ml) at pH 6.5. 2N Sodium nitrite was added (6.5ml) and the solution was poured onto ice and concentrated HCl (4 ml) anddiazotised at 10-20° C. for 2 hours. Excess nitrous acid was destroyedusing sulphamic acid to give a diazo solution.5,5'-Dihydroxydinaphth-2,2'-urea-7,7'-disulphonic acid (2.75 g) wasdissolved in water (75 ml) and tetrahydrofuran (50 ml), added to theabove diazo solution and stirred at room temperature, pH 6.5 overnight.The solution was acidified to pH 2.5 and screened to remove excessdiazo, and the product was precipitated out by the addition ofisopropanol. On drying this gave the title product as a dark red solid(6.60 g) with a λmax at 540 nm.

Stage (b)--Dyeing

The title dye (0.10 g) was dissolved in pH 7 buffer solution containinga 5 g piece cotton (30 ml) and heated from 30° C. to 95° C. at 1degC.min⁻¹. After 15 minutes Na₂ SO₄ (0.75 g) was added followed an hourlater by 2 ml of a 0.05M solution of tris(2-aminoethyl)amine. The bathwas maintained at 95° C. for a further hour. The exhausted dyebath wasessentially colourless and the cotton was dyed a dull bluish-red shade.

EXAMPLE 12

The method of Example 11 was repeated except that in place ofmeta-toluidine there was used 3-acetamido-6-sulpho aniline, and in placeof 5,5'-dihydroxydipnaphth-2,2'-urea-7,7'-disulphonic acid there wasused the coupling component from Example 2. The resultant bluish-redsolid had a λmax at 537 nm.

EXAMPLE 13 ##STR17## Stage (a)

J-Acid (23.4 g) was dissolved in water (250 ml) at pH 7 and cooled to0-5° C. Terephthaloyl chloride (10.2 g) in acetone (100 ml) was addeddropwise to this solution, and after stirring at 0-5° C. and pH 6 for 4hours, the mixture was allowed to warm to room temperature. A smalladditional portion of terephthaloyl chloride (0.50 g) in acetone (20 ml)was added and after stirring for a further hour the product was filteredoff and washed with acetone. This gave 33.5 g of a coupler.

3-(β-sulphatoethylsulphonyl)aniline (1.55 g) was dissolved in water (50ml) at pH 6, and 2N sodium nitrite (3 ml) was added. This was added toice and concentrated HCl (1.6 ml) and diazotised at 0-5° C. for 1 hour.Excess nitrous acid was destroyed by adding sulphamic acid.

The above coupler (1.80 g) was dissolved in a mixture of water (75 ml)and acetone (75 ml) and added dropwise to the diazo at pH 3. Thesolution was stirred at 0-5° C. pH 3-3.5 for 4 hours then allowed towarm to room temperature. Sufficient isopropanol was added to causeprecipitation and the product was filtered off and dried to give thetitle dye (3.0 g) having a λmax at 478 nm.

Stage (b)

The title dye (0.03 g) was dissolved in water (14 ml) and 2M Na₂ CO₃ (2ml) was added. Sufficient N(CH₂ CH₂ NH₂)₃ (0.05M solution) was added togive a 3:1 Nu:Dye ratio. 5 g of cotton was impregnated with thesolution, excess solution was squeezed out of the cotton and it waswrapped in polythene and left at room temperature for 24 hours. The dyewas fixed very firmly to the cotton and little coloured was washed out,even when the dyed cotton was heated in boiling water.

EXAMPLE 14

The method of Example 13 was repeated except that in place of3-(β-sulphatoethylsulphonyl)aniline there was used4-(β-sulphatoethylsulphonyl)aniline.

EXAMPLE 15

The method of Example 11 was repeated except that in place of4-(β-sulphatoethylsulphonyl)aniline there was used3-(β-sulphatoethylsulphonyl)aniline.

EXAMPLE 16

The method of Example 10 was repeated except that in place of2-methoxy-5-(β-sulphatoethylsulphonyl)aniline there was used4-(β-sulphatoethylsulphonyl)aniline.

EXAMPLE 17 ##STR18## Stage (a)

Cyanuric chloride (4.06 g) was dissolved in acetone (30 ml) and added toice/water (50 ml). A solution of J-acid in water (100 ml) at pH 7 wasadded dropwise and the reaction was stirred, maintaining the mixture at0-5° C., pH 2-2.5 until it was negative to Ehrlich's reagent.

4-(β-sulphatoethylsulphonyl)aniline (5.62 g) was dissolved in water (50ml) at pH 7 and 2N sodium nitrite (11 ml) was added. This solution waspoured onto ice and concentrated HCl (6 ml) and diazotised for 1 hourbefore destroying excess nitrous acid using sulphamic acid. The diazoproduct was then added to the above suspension of J-aciddichlorotriazine and the mixture was stirred at pH 3-4, 0-5° C. for 3hours. A solid was isolated by precipitation with isopropanol andfiltering.

The above solid (5 g) was dissolved in water (100 ml).p-phenylenediamine (0.37 g) in water (50 ml) was added and the solutionwas stirred at pH 4-5 and room temperature for 20 hours. Sufficientethanol was added to cause precipitation and the dye was filtered-offand dried. The title product was obtained as an orange solid with a λmaxat 480 nm.

EXAMPLE 18

The method of Example 40 was repeated except that in place of1,4-phenylene diamine there was used a compound of the formula:##STR19##

EXAMPLE 19

The method of Example 2 was repeated except that in place of4-(β-sulphoatoethylsulphonyl)aniline there was used2-amino-6-(β-sulphatoethylsulphonyl)naphthalene. The product had a λmaxat 493 nm.

EXAMPLE 20

The method of Example 1 was repeated except that in place of4-(β-sulphatoethylsulphonyl)aniline there was used4-methoxy-3-(β-sulphatoethylsulphonyl)aniline.

EXAMPLE 21 ##STR20## Stage (a)

Cyanuric chloride (3.69 g) was dissolved in acetone (30 ml) and added toice/water (50 ml). A solution of 4-(β-sulphatoethylsulphonyl)aniline(5.62 g) in water at pH 6 was added dropwise, keeping the reactionmixture at pH2. This was stirred for 2 hours at 0-5° C. The mixture wasallowed to warm to room temperature and a pH 6 solution of J-acid (4.70g) in water (50 ml) was added dropwise. The solution was stirred at pH 6overnight, and the coupler was isolated by removing the water underreduced pressure.

Stage (b)

4-(β-sulphatoethylsulphonyl)aniline (28.1 g) was dissolved in water (150ml) at pH 6, 2N sodium nitrite was added (55 ml) and the mixture waspoured slowly onto ice and concentrated HCl (25 ml). After diazotisingat 0-5° C. for 2 hours, excess nitrous acid was destroyed by theaddition of sulphamic acid. 5-Acetamidoaniline-2-sulphonic acid (23.0 g)was dissolved in water (150 ml) at pH 6 and cooled in ice. This wasslowly added to the diazo solution and the mixture was stirred at pH3.5, 0-5° C. for 2 hours before allowing to warm to room temperature.The solution was adjusted to pH 1.5, and the product was filtered offand dried.

Stage (c)

The product from stage (b) (2.35 g) was dissolved in water at pH 6 and2N sodium nitrite (2.4 ml) was added. The solution as added to ice andconcentrated HCl (1.5 ml) and diazotised for 1 hour at 0-5° C. Excessnitrous acid was destroyed using sulphamic acid.

The coupler from stage (a) (2.93 g) was dissolved in water (50 ml), andthe diazo was added to this and then stirred at 0-5° C., pH 3-4 for 2hours. The solution was warmed to room temperature adjusted to pH 2.5and filtered. The product was purified by redissolving in water (100 ml)and adding salt (20% w/v). The resultant title product was filtered offand dried to give a bluish-red solid with λmax at 526 nm.

EXAMPLE 22

The title dye from Example 1 (0.10 g) was dissolved in a dyebathcontaining pH 7 buffer solution (30 ml), a 5 g piece of cotton wasadded, and the bath was heated to 95° C. at 1 degC.min⁻¹. After 15minutes at 95° C., Na₂ SO₄ (0.75 g) was added, followed an hour later by1,4-diaminopiperazine (0.017 g). The bath was kept at 95° C. for afurther hour. The resultant dyebath was only weakly coloured and thecotton was dyed a bright orange.

EXAMPLE 23

The title dye of Example 10 (0.05 g) and the title dye of Example 4(0.05 g) were dissolved in a dyebath containing pH 7 buffer solution (30ml) and a 5 g piece of cotton. The bath was heated to 90° C. at 1degC.min⁻¹, left for 15 minutes, then Na₂ SO₄ (0.75 g) was added. Aftera further 1.5 hours at 95° C., tris(2-aminoethyl)amine (0.022 g) wasadded and heating was continued at 90° C. for 1 hour. The resultantdyebath was essentially colourless and the cotton was dyed a dullmid-red with excellent wet fastness.

EXAMPLE 24 ##STR21##

A solution of cyanuric chloride (0.06M, 11.1 g) in acetone (100 ml) wasadded over 5 min to a solution of 3-(β-sulphatoethylsulphonyl)aniline(0.06M, 16.9 g) in water (100 ml) at pH 6 and 0-5° C. After stirring for1 hour, the solution was added to a solution of the triphenodioxazinedyebase described in U.S. Pat. No. 3,996,221, Column 11, lines 17-19(66.4 g, 19% strength) in water (400 ml) and N-methyl pyrrolidone (400ml) at pH 10. The mixture was stirred for 4 hours at pH 9. Isopropanol(21) was added and the precipitated product was filtered off, washedwith isopropanol and air-dried to give the title product (24.5 g) μmax636 nm.

When the title product was applied to cotton by exhaust dyeing withtris(2-aminoethyl)amine the dyebath was left only weakly coloured.

EXAMPLE 25

The method of Example 24 was repeated except that in place of3-(β-sulphatoethylsulphonyl)aniline there was used4-(β-sulphatoethylsulphonyl)aniline.

EXAMPLE 26

The method of Example 5 was repeated except that in place of 3-methylaniline there was used 3-acetamido aniline. The resultant dye gave animmobilisation of 99.5% in the immobilisation test.

EXAMPLE 27 Stage (a)--Preparation

The method of Example 5 was repeated except that in place of 3-methylaniline there was used 3-acetamido aniline. The resultant product had aλmax at 421 nm.

Stage (b)--Dyeing

The resultant dye (0.1 g) was dissolved in water (50 ml). Cotton (5 g)was added followed by NaCl (1.25 g). The mixture was heated at 95° C.for 1 hour then cooled to 60° C. Na₂ CO₃ (1 g) was added and heating at60° C. was continued for 1 hour. The cotton was dyed a brightreddish-yellow shade and had good fastness properties, together with anoutstanding level of fixation.

EXAMPLES 28-37

The method of Example 5 was repeated except that 3-methyl aniline wasreplaced by the amines listed in Table 1 below. The λmax (nm) measuredis also given

                  TABLE 1                                                         ______________________________________                                        Exam-                                                                         ple   Amine                      0 max                                        ______________________________________                                        28    2,4-diamino benzene sulphonic acid                                                                       442 nm                                       29    N-(β-aminoethyl)-2-hydroxy-3-carbonamido-4-methyl                                                   456 nm                                             pyridone                                                                30    1-(2-methyl-3-amino-5-sulphophenyl)-3-carboxy-                                                           466 nm                                             pyrazol-5-one.                                                          31    1-(4-aminophenyl)-3-methyl-pyrazol-5-one                                                                 436 nm                                       32    p-amino acetoacetanilide   416 nm                                       33    N-methyl aniline           388 nm                                       34    3-amino benzyl alcohol     407 nm                                       35    1-amino-7-sulphonaphthalene                                                                              484 nm                                       36    3-methoxy aniline          419 nm                                       37    2,5-dimethyl aniline       461 nm                                       ______________________________________                                    

EXAMPLE 38

The method of Example 5 was repreated except that in place of4(β-sulphatoethylsulphonyl)aniline there was used4-amino-N-(β-sulphatoethyl)phenyl sulphonamide. The resultant producthad a αmax at 420 nm.

EXAMPLE 39 Stage (a)

2-aminonaphthalene-1-sulphonic acid (0.08 mol) was added in portions tochlorosulphonic acid (50.0 ml) with stirring such that the temperatureremained <35° C. The mixture was stirred at 35° C. for 20 hours. Afterthis time the cooled reaction mixture was added dropwise to ice/water(200 ml) such that the temperature remained <10° C. The resultingprecipitate was collected and washed with cold water. The resultingpaste (0.08 mol) was added slowly with cooling to a solution of ethylenediamine (0.04 mol) in water (250 ml) such that the temperature remainedin the range of 0-5° C. The pH of the resulting mixture was raised to pH10 by the addition of 2N sodium hydroxide solution. The mixture wasmaintained at this pH while stirring at 0-5° C. for 2 hours. After thistime the mixture was acidified to pH1 and the resulting precipitatecollected and washed with acetone to yield a solid product.

Stage (b)

A solution of cyanuric chloride (0.1 mol) in acetone (100 ml) was addeddropwise to a stirred solution of p-aminobenzene sulphatoethyl sulphone(0.1 mol) in water (300 ml) containing calsolene oil at pH 5 and 0-5° C.The mixture was stirred at 0-5° C. for 1 hour. After this time asolution of J-acid (0.1 mol) in water (300 ml) at pH 6 was added and thepH adjusted to pH 6.5. The mixture was stirred and allowed to warm toroom temperature over 17 hours while maintaining the pH at 6.5. Afterthis time isopropanol (1000 ml) was added and the resulting oilseparated and triturated with methylated spirits yielding a solidproduct.

Stage (c)

The product of stage (a) (0.002 mol) was dissolved in water (20.0 ml) atpH 7. The solution was cooled to 0-5° C. and treated with 2N sodiumnitrite solution (0.0044 mol) followed by concentrated hydrochloric acid(2.2 ml) and the mixture stirred at this temperature for 30 minutes.After this time excess nitrite was destroyed by the addition ofsulphamic acid (2.2 ml). A solution of the product of stage (b) (0.004mol) in water (50.0 ml) was added and the pH was raised slowly to 6.5 bythe addition of 2N sodium carbonate solution. The pH was maintained at6.5 and temperature of 0-5° C. for 1 hour and then allowed to warm toroom temperature over 17 hours. The resulting precipitate was collectedand dried in vacuo yielding the dye: ##STR22##

EXAMPLE 40 Stage (a)

2-aminonaphthalene-1-sulphonic acid (0.04 mol) was added in portions tochlorosulphonic acid (25.0 ml) with stirring such that the temperature<35° C. The mixture was stirred at 35° C. for 20 hours. After this timethe cooled reaction mixture was added dropwise to ice/water (200 ml)such that the temperature <10° C. The resulting precipitate wascollected and washed with cold water. The resulting paste (0.04 mol) wasdissolved in acetone/water (170/30) (200 ml). To this solution was addedp-phenylene diamine (0.02 mol) and sodium acetate (13.1 g) and theresulting mixture stirred at room temperature for 17 hours. After thistime the resulting precipitate was collected and purified byrecrystallisation twice from water yielding a solid product.

Stage (b)

p-aminobenzene sulphato ethylsulphone (0.06 mol) in water (100 ml)containing calsolene oil (3 drops) at pH5 was treated with a solution ofcyanuric chloride (0.066 mol) in acetone (100 ml) dropwise such that thetemperature was 0-5° C. The pH was maintained at pH 5 by addition of 2NNa₂ CO₃ solution. The mixture was stirred at 0-5° C. for 1 hour.1-hydroxy-8-aminonaphthalene-3-sulphonic acid (0.06 mol) in water (50.0ml at pH 7 was added and the mixture stirred at room temperatureovernight. The pH of the mixture was allowed to fall to pH2. After thistime the pH of the mixture was adjusted to pH7 and stirred for a further1 hour. Methylated spirits (400 ml) was added and the resultingprecipitate collected, washed with methylated spirits and dried in vacuoyielding a solid product.

Stage (c)

A solution of the product of stage (a) (0.002 mol) was dissolved inwater (20.0 ml) at pH7. A solution of 2N sodium nitrite (2.2 ml) wasadded and the mixture cooled to 0-5° C. The solution was treated withconcentrated hydrochloric acid (2.2 ml) and the mixture stirred at 0-5°C. for 2 hours. After this time the excess nitrite was destroyed by theaddition of sulphamic acid (2.0 ml). A solution of the product of stage(b) (0.004 mol) in water (50.0 ml) was added and the pH was raisedslowly to 6.5 by the addition of 2N sodium carbonate solution. Themixture was maintained at pH 6.5 and stirred at 0-5° C. for 2 hours andthen allowed to warm to room temperature over 17 hours. After this timemethylated spirits was added and the resulting precipitate collected anddried in vacuo yielding the dye: ##STR23##

EXAMPLES 41 TO 62

The dyeing of cotton with differing dyes and nucleophilic agents wasinvestigated using the following method.

Dye (0.1 g) was dissolved in water (50 ml) and pH adjusted to pH 5.5.Cotton (5 g) was added followed by sodium sulphate (1.25 g) and themixture heated at 95° C. for 1 hour. Sodium hydrogen carbonate (0.25 g)was then added before heating at 95° C. for a further 30 minutes. Thenucelophilic agent (sufficient such that the ratio of nucleophilicgroups in the nucelophilic agent to electrophilic groups in the dye was1.5:1) was then added and the mixture heated at 95° C. for 1 hour.

The cloth was removed from the dyebath and excess liquor wrung from it.The cloth was rinsed with aqueous acetic acid (1 gl⁻¹) (45 ml), boiledwith water twice (50 ml for 15 minutes each) and finally rinsed withcold water (50 ml). The dyebath and the wash liquors were combined and aspectrophotometric assessment of all unfixed colour made.

% Fixation was calculated from the formula:

    % Fixation=[Concentration of dye in dyebath before]-[Concentration of dye in dyebath after]/[Concentration of dye in dyebath before]×100

Dyes employed were those of Examples 25, 27 and 39. The nucelophilicagents were selected from those in Table 2 below.

                  TABLE 2                                                         ______________________________________                                        Nuchleophilic agent   Number                                                  ______________________________________                                        Ethylene diamine      1                                                       Hexamethylene diamine 2                                                       Piperazine            3                                                       2,5-dimethyl piperazine                                                                             4                                                       2-amino-4-(2-amino ethylamino)aniline                                                               5                                                       1,2,4-triamino benzene                                                                              6                                                       Diethylene triamine   7                                                       Tetra ethylene pentamine                                                                            8                                                       Tris (2-aminoethyl)amine                                                                            9                                                       ______________________________________                                    

The combination of dyes and nucelophilic agents employed, and thefixation achieved (%) are given in Table 3 below.

                  TABLE 3                                                         ______________________________________                                        Example No                                                                            Dye         Nucleophilic agent                                                                         % Fixation                                   ______________________________________                                        41      Example 25  1            71                                           42      Example 25  2            94                                           43      Example 25  3            67                                           44      Example 25  4            66                                           45      Example 25  5            68                                           46      Example 25  6            70                                           47      Example 25  7            85                                           48      Example 25  8            96                                           49      Example 27  1            99.98                                        50      Example 27  2            99.96                                        51      Example 27  3            99.98                                        52      Example 27  4            99.92                                        53      Example 27  5            99.26                                        54      Example 27  6            99.22                                        55      Example 27  7            99.99                                        56      Example 27  8            99.92                                        57      Example 39  2            94                                           58      Example 39  8            94                                           59      Example 39  9            95                                           60      Example 40  2            89                                           61      Example 40  8            89                                           62      Example 40  9            90                                           ______________________________________                                    

EXAMPLE 63-74

Cotton may be dyed employing the following, the general method given inExample 5, stage (c), with the dye and nucelophilic agent being variedas detailed in Table 4. In Table 4 PEI=polyethylene imine; JEFFAMINE isa Trademark for a range of commercially available amines.

                  TABLE 4                                                         ______________________________________                                        Example No   Dye          Nucelophilic Agent                                  ______________________________________                                        63           ex-Example 5 PEI 600                                             64           ex-Example 5 PEI 1800                                            65           ex-Example 6 PEI 60,000                                          66           ex-Example 7 JEFFAMINE D2000                                     67           ex-Example 27                                                                              PEI 600                                             68           ex-Example 27                                                                              PEI 1800                                            69           ex-Example 27                                                                              PEI 60,000                                          70           ex-Example 27                                                                              JEFFAMINE D2000                                     71           ex-Example 30                                                                              PEI 100,000                                         72           ex-Example 31                                                                              JEFFAMINE ED900                                     73           ex-Example 32                                                                              JEFFAMINE T5000                                     74           ex-Example 33                                                                              PEI 1000                                            ______________________________________                                    

EXAMPLES 75-85

Cotton may be dyed by the following general method.

A composition is prepared comprising the dye (0.1 g), water (50 ml) and0.0072 g of nucleophilic agent. Cotton (5 g) is added and thetemperature raised to 50° C. Salt (1 g) and sodium bicarbonate are addedand the temperature raised to 58° C. and held at this temperature for 1hour thereby causing the dye and nucleophilic agent to join together.The cotton is removed, rinsed in water then boiled in detergent to givedyed cotton.

Details of the dyes and nucleophilic agents which may be employed aregiven in Table 5 below.

                                      TABLE 5                                     __________________________________________________________________________    Example No                                                                           Dye     Nucelophilic agent                                             __________________________________________________________________________    75     ex Example 5                                                                          Trithiotriazine                                                76     ex Example 6                                                                          1 #STR24##                                                     77     ex Example 7                                                                          2 #STR25##                                                     78     ex Example 27                                                                         3 #STR26##                                                     79     ex Example 28                                                                         4 #STR27##                                                     80     ex Example 29                                                                         5 #STR28##                                                     81     ex Example 30                                                                         6 #STR29##                                                     82     ex Example 31                                                                         7 #STR30##                                                     83     ex Example 32                                                                         8 #STR31##                                                     84     ex Example 27                                                                         9 #STR32##                                                     85     ex Example 27                                                                         Trithiotriazine                                                __________________________________________________________________________

We claim:
 1. A process for the coloration of a substrate comprisingapplying thereto a water-soluble dye having at least two electrophilicgroups and a nucleophilic agent having a molecular weight below 600 andat least one group selected from thiols, thiones, aliphatic primaryamino groups and aliphatic secondary amino groups, said dye being a dyeof Formula (1) or a salt thereof: ##STR33## wherein: each Q¹independently is an electrophilic group selected from halogen, sulphoand quaternary amonium or a non-electrophilic group of formula --NR⁷ R⁸and --OR⁷ wherein R⁸ is H or alkyl and R⁷ is H, optionally substitutedalkyl or optionally substituted aryl;each T independently is --O--,--S-- or --NR^(a) ; each L¹ independently is a divalent organic linkergroup; each V¹ independently is an electrophilic vinyl sulphone group, agroup which is convertible to an electrophilic vinyl sulphone group ontreatment with aqueous alkali or an electrophilic group of formula --SO₂NHCH₂ CH₂ --Y wherein Y is --OSO₃ H, --SSO₃ H, --Cl or --OCOCH₃ ; eachR^(a) independently is H or optionally substituted alkyl; Z is anoptionally substituted buta-1,3-dione phenylene, naphthylene orheterocyclic group; and m and n are each independently 0 or 1; andwherein the electrophilic groups in the water-soluble dye react with thethiol, thione, aliphatic primary amino group or aliphatic secondaryamino group in nucleophilic agent.
 2. A process according to claim 1wherein the nucleophilic agent having a molecular weight below 600 hasat least two groups selected from aliphatic primary amino groups andaliphatic secondary amino groups.
 3. A process according to claim 1 or 2for the coloration of a substrate comprising the steps:(a) applying anaqueous solution of the dye to the substrate; (b) bringing thenucleophilic agent into contact with the substrate.
 4. A processaccording to claim 1 wherein the electrophilic groups in thewater-soluble dye react with the aliphatic primary amino group(s) oraliphatic secondary amino group(s) in the nucleophilic agent.
 5. Aprocess according to claim 1 wherein the water-soluble dye is a reactivedye and the process for coloration is performed under conditions suchthat the dye does not react to a significant extent with the substratebefore it reacts with the nucleophilic agent.
 6. A compositioncomprising:(i) a water-soluble dye having at least two electrophilicgroups; and (ii) a nucleophilic agent having a molecular weight below600 and at least one group selected from thiols, thiones, aliphaticprimary amino groups and aliphatic secondary amino groups where saidamino groups are optionally masked using a protecting group, said dyebeing a dye of Formula (1) or a salt thereof: ##STR34## wherein: each Q¹independently is an electrophilic group selected from halogen, sulphoand quaternary amonium or a non-electrophilic group of formula --NR⁷ R⁸and --OR⁷ wherein R⁸ is H or alkyl and R⁷ is H, optionally substitutedalkyl or optionally substituted aryl; each T independently is --O--,--S-- or --NR^(a) ; each L¹ independently is a divalent organic linkergroup; each V¹ independently is an electrophilic vinyl sulphone group, agroup which is convertible to an electrophilic vinyl sulphone group ontreatment with aqueous alkali or an electrophilic group of formula --SO₂NHCH₂ CH₂ --Y wherein Y is --OSO₃ H, --SSO₃ H, --Cl or --OCOCH₃ ; eachR^(a) independently is H or optionally substituted alkyl; Z is anoptionally substituted buta-1,3-dione phenylene, naphthylene orheterocyclic group; and m and n are each independently 0 or
 1. 7. Awater-soluble dye of Formula (I) and salts thereof having at least twoelectrophilic groups: ##STR35## wherein: each Q¹ independently is anelectrophilic group selected from halogen, sulpho and quaternary amoniumor a non-electrophilic group of formula --NR⁷ R⁸ and --OR⁷ wherein R⁸ isH or alkyl and R⁷ is H, optionally substituted alkyl or optionallysubstituted aryl;each T independently is --O--, --S-- or --NR^(a) --;each L¹ independently is a divalent organic linker group; each V¹independently is an electrophilic vinyl sulphone group, a group which isconvertible to an electrophilic vinyl sulphone group on treatment withaqueous alkali or an electrophilic group of formula --SO₂ NHCH₂ CH₂ --Ywherein Y is --OSO₃ H, --SSO₃ H, --Cl or --OCOCH₃ ; each R^(a)independently is H or optionally substituted alkyl; Z is an optionallysubstituted buta-1,3-dione phenylene, naphthylene or heterocyclic group;and m and n are each independently 0 or
 1. 8. A dye according to claim 7wherein Z is an optionally substituted 1,3-phenylene or 1,4-phenylenegroup.
 9. A dye according to claim 7 of the Formula (2) and saltsthereof: ##STR36## wherein: each R^(b) independently is H or C₁₋₄-alkyl;G is H, alkyl, alkoxy, amido, ureido, halo, nitro, carboxy, aminoor sulpho; each Q² independently is F, Cl, or a quaternary ammoniumgroup; and each V² independently is a vinyl sulphone group or a groupwhich is convertible to a vinyl sulphone group on treatment with aqueousalkali, or a group of formula --SO₂ NHCH₂ CH₂ --Y wherein Y is --OSO₃ H,--SSO₃ H, --Cl or --OCOCH₃, or a group of formula --NHCOCR^(b) ═CH₂ or--NHCOCBr═CH₂.
 10. A dye according to claim 9, wherein G represents anacetamido group.